Glass fiber binder composition containing tall oil pitch



United States Patent 3,244,580 GLASS FIBER BENDER COMPOSITIGN CONTAININGTALL OIL PITCH Joseph P. Stalego, Newark, Ohio, assignor to Owens-Corning Fiberglas Corporation, a corporation of Delawere No Drawing.Filed Aug. 21, 1959, Ser. No. 835,291 3 Claims. (Cl. 161-170) Thisinvention relates to a binder composition, and, more particularly, tosuch a composition that is especially adapted for use in connection withglass or other vitreous fibers.

The production of wool-like and board-like masses of intermeshed glassand other vitreous fibers is an important industry. Wool-like masses ofsuch fibers are produced by drawing streams of molten glass from asuitable body thereof through small diameter orifices, attenuating thestreams to provide a desired fiber diameter or average fiber diameter,projecting the resulting fibers and a suitable binder composition onto aforaminous conveyor, and advancing the collected fibers through asuitable curing oven to cause hardening of the binder composition.Board-like masses of such fibers are produced in a similar manner,except that the final curing is carried out while the mass of fibers iscompressed in a desired shape, so that the binder cures or hardens inthe environment of a densified mass of the fibers, and

locks them in such densified condition.

Phenolic resins, usually of the phenolformaldehyde type, have been foundto be admirably suited in binder compositions for use with glass andother vitreous fibers, particularly when used in conjunction with apinewood pitch extract to improve the flow characteristics 1 of thephenolic resin. It has been found, however, that a pinewood pitchextract tends to increase the rate of cure of a binder composition inwhich it is used. While this may be advantageous to a limited extent,because the desired final cure of the binder composition is accelerated,it is not possible to use an excessively rapid curing binder compositionwith glass fibers because such a composition will cure so fast when itis associated with fibers and heated that it will not flow tofiber-tofiber junctures where it is required to be effective as .abinder. In addition, a binder which cures at an excessively rapid ratetends to collect on the hot walls of a forming hood, Where its presenceconstitutes a fire hazard and necessitates frequent cleaning. As aconsequence of the characteristic of a pinewood pitch extract 1 A binderis usually associated with glass or other vitreous fibers in a forminghood, being projected with the fibers through a compressible fluid.usually air, onto a foraminous conveyor. The binder is heated by hotfibers, or by hot fluid or by both. Studies of the phenomena involvedwithin the forming hood and on the conveyor indicate that a bindercoinposition sprayed into the forming hood is applied to the fibersprincipally by filtration from the compressible fluid onto a wool likemass of the fibers collecting on the conveyor. After the bindercomposition is deposited on the fibers, it must flow to fiber-to-fiberjnnctures in order to be effective as a binder, when cure is completed.The flow characteristics of a binder composition can be evaluated bymeans of a test which is subsequently described in more detail, andwhich involves depositing a predetermined quantity thereof on a hotplate and measuring the dimensions of the deposited composition aftercure proceeds to such an extent that no further flow occurs.

of increasing the rate of cure of a phenolic binder composition, theamount thereof which .it has heretofore been possible to use to improvethe flow characteristics of the binder composition has been limited.

The present invention is based upon the discovery that various tall oilpitches can be used as constituents of phenolic binder compositions foruse with glass or other vitreous fibers, and that such .pitches have thedesirable characteristic of retarding the rate of cure of thecomposition without disadvantageously afiecting the flow characteristicsthereof. Such pitches can be used with or without pinewood pitchextracts, but are preferably employed in conjunction with the extractsto obtain compositions combining an optimum of flow characteristics andcure rate.

It is, therefore, an object of the invention to provide an improvedphenolic resin binder composition.

It is a further object of the invention to provide an improved phenolicresin binder composition comprising a tall oil pitch.

It is a further object of the invention to provide a method forproducing a mass of intermeshed glass or other vitreous fibers bondedtogether at points of contact by an improved phenolic binder compositionin a cured or hardened condition.

Other objects and advantages will be apparent from the description whichfollows, which is intended only :to illustrate and disclose, and in noway to limit, the invention.

According to the invention an improved heat hardenable phenolic resinbinder composition is provided. Such a composition has a solids contentfrom about .3 percent 2 to about 24 percent, and is an aqueousdispersion consisting essentially of a heat hardena'ble phenolic resin,and a cure controlling composition comprising, per parts of the phenolicresin, from 5 parts to 100 parts of a tall oil pitch and not more than100 parts of a pinewood pitch extract. The heat hardenable phenolicresin is one selected from the group consisting of phenolformaldehydecondensation products and phenol-amino compound-formaldehydecondensation products, and is of the resole type. The tall oil pitch isone having a flash point from 400 F. to 550 F.

The invention will be more fully understood by reference to thefollowing examples, which are presented solely for the purpose ofillustrating and disclosing, and

The terms percent and parts are used herein, and in the appended claims,to refer to percent and parts by weight, unless otherwise indicated.

Tall oil is a 'by-product of the paper making industry; tall oil pitchis a commercially available residue left after distillation of crudetall oil to recover rosin acids and tall 011 fatty acids. Tall oilpitches have the following properties:

Acid number 40-160 Percent rosin acids 0.5-20 Percent fatty acids 780Saponification number -1'65 Percent unsaponifiables 20-35 Flash point,F. In general, a pitch can be identified by its flash point. whichvaries as a direct function of percent rosin acids and as an inversefunction of percent fatty acids.

are in no way to be construed as limitations upon, the

invention.

EXAMPLE 1 A binder composition was prepared in a mixing tank providedwith a propeller-type agitator, which tank was first charged with 800parts of water, and the water and subsequently charged ingredients werestirred during the formulation of the binder composition. An 83 partportion of a Phenolic Resin A was then added, followed by 171 parts of atall oil pitch-pinewood pitch extract composition B 7 /2 parts of 28percent ammonium hydroxide, 22 parts of mineral oil emulsified withstearic acid and ammonium carbonate, 0.7 part of ammonium sulfate, and0.03 part of gamma-aminopropyl-triethoxysilane. Agitation was continuedfor five minutes after the silane addition to assure substantialuniformity of the completed binder composition.

The binder composition produced as described in the preceding paragraphwas sprayed into a forming hood through which glass fibers were beingprojected onto a foraminous conveyor. The fibers were collected in theform of a wool-like mass associated with the binder composition. Therelative proportions of binder composition and fibers were such that thebinder, after cure thereof, constituted slightly in excess of 8 percentof the total wool-like mass. Cure was accomplished in an oven maintainedat a temperature of about 400 F. through which the glass fibers andassociated binder were passed in a period of about one 6 minute.Examination of the woollike product which was produced, after cure ofthe binder composition, indicated that the composition had flowedsatisfactorily to areas of fiber-to-fiber contact, so that the tall oilpitch-pinewood pitch extract composition B had neither undulyaccelerated the cure of Phenolic Resin A nor disadvantageously affectedthe flow characteristics thereof.

The eifect of the tall oil pitchinewood pitch extract composition B uponflow characteristics of Phenolic Resin A and upon gel time of PhenolicResin A were also determined by an independent series of tests. Forthese tests, a special tall oil pitchinewood pitch extract composition B(30 percent) 7 was prepared. Several compositions Phenolic resin A wasan aqueous dispersion of phenolformaldehyde condensation products,solids content 41.5 percent. The production thereof is subsequentlydescribed in detail.

The composition was an aqueous dispersion containing, per 100 partsthereof, 20%. parts of tall oil pitch having a flash point ofsubstantially 530 F. and 20 parts of pinewood pitch extract. Thepinewood pitch extract that was used is resinous in nature and can beisolated as described in US. Patent 2,391,368 (page 2, column 1, line 34and following). It had the following analysis 6 percent high meltingfurfural condensate (methanol insoluble). 4 percent neutral oils(hydrocarbons esters and others). 9 percent rosin. 5 percentbelrophenol-lactone (probably C1sH1403.2 (OCHSOH) (possibly aboutDepending upon the product desired, the optimum cure temperature maydeviate somewhat from 400 F., and oven time may vary from about oneminute to about five minutes.

This composition was identical with the previously de scribedcomposition B. except that it had a 30 percent solids content instead ofa 25 percent solids content.

*Notdn accordance with the invention; presented for purposes ofcomparison.

Flow characteristics of compositions 1 through 4 were then checked bycharging a burette with a 5 cc. portion of each, discharging each 5 cc.portion onto the center of a hot plate maintained at a temperature ofC.,

and, after the composition had cured to a hardened con-- dition,measuring the diameter of the cured resin film in two directions atright angles to one another. Gel time of each of the compositions wasdetermined by charging a burette with a 2 cc. portion of each, flowingthe charge onto a hot plate maintained at 150 C., and determining thetime required for each composition to cure, on the hot plate, to acondition at which strings formed from the sample when patted with aspatula. The results of these tests are presented in Table II, below:

TABLE II Flow characteristics diamctcr of cured film in inches Gel timein seconds First Second direction direction Composition 1 3% 3% 185Composition 2 3 3% 300+ Composition 3. 3% 4 116 Composition 4 3 3% 122*This composition was not fully gelled after 300 seconds.

Phenolic Resin A was prepared from parts of formalin, or 37 percentwater solution of formaldehyde, 100 parts of phenol and 4 parts ofsodium hydroxide. The starting materials were mixed in a suitablevessel, allowed to stand at room temperature (about 25 C.) forapproximately 16 hours, and heated at a progressively increasingtemperature which was sufficient to maintain gentle boiling thereof.Heating was discontinued when the temperature of the reaction mixturereached approximately 85 C. The sodium hydroxide in the reaction mixturewas then neutralized with phosphoric acid, and the neutralized resin wasfiltered.

It has also been determined that as little as 5 percent of tall oilpitch, based upon total solids of Phenolic Resin A, is effective toincrease the gel time thereof, and without appreciable effect upon theflow characteristics thereof. On the indicated basis, 10 percent, 21percent and 26.5 percent of the tall oil pitch have been added toPhenolic Resin A, and gel time has been found to be a direct function ofthe percent of tall oil pitch used, while flow characteristics have beenfound to remain substantially unchanged.

EXAMPLE 2 Various binder composions other than those described inExample 1, above, have been produced in the manner set forth and havebeen used as described in Example 1 in producing wool-like andboard-like bodies of. intermeshed glass fibers. Data concerningrepresentative ones of such binder compositions is set forth in TableIII, below:

TABLE III Binder composition No. Composition in parts Water 687 761 369431 Phenolic Resin A. 371 358 197 Phenolic Resin B* i 246 198 Tall oilpitch-pinewood extract Composition B 43 458 281 140 70 Ammoniumhydroxide (28 percent) 4% 15 2% 6 Mineral oil emulsified with stearicacid and ammonium carbonate 30 40 25 10 10 Ammonium sulfate 1.4 l- 5 1Gamma-aminopropyltriethoxysilane .i 0.1 x 0.1 Red dye 0.5 0.1

*Phenolie resin B was produced by charging a reaction vessel with 58parts of phenol, 123.4 parts of formalin, and 12 parts of barium hydrate(Ba(0H) .8H2O), and heating the resulting charge for a total of 10 hoursduring which time it was stirred by a propeller-type agitator. Thecharge was first heated to 110 F., and maintained at about suchtemperature for approximately 3 hours, heated to and held atapproximately 120 F. for an additional hours, and then heated to andheld at about 140 F. for the remaining 2 hours. The reaction productswere then cooled to approximately 100 F., and neutralized with sulfuricacid to a pH of about 7.5. A 23.2 part charge of melamine was then addedto the neutralized reaction products, and the resulting mixture washeated to and maintained at approximately 140 F. for an additional 2hour period. The reaction products were then cooled to approximatelyroom temperature of 75 F., and neutralized with further sulfuric acid toa pH of approximately 7.2.

Excellent results have also been achieved using, instead of PhenolicResins A and B, identified above, phenolic compositions producedsimilarly to Resin B, but using various proportions of urea instead ofall or a part of the melamine in producing phenol-amino compoundaldehydeproducts. Dicyandiamide urea borate and guanidine can be substituted forall or part of the urea, and substituted melamines can be used in placeof at least a part of the melamine with excellent results.

The phenolic resin, water and the cure-controlling composition (tall oilpitch or tall oil pitch plus pinewood pitch extract) an: the essentialconstituents of the aboveidentified binder compositions. Bindercompositions including these essential constituents have been found tobe unexpectedly stable and non-abrasive, as well as free from settling,by comparison with previously known compositions. The ammoniumhydroxide, emulsified mineral oil, ammonium sulfate, silane and dye areused in some instances to control a particular property or properties ofa finished product, but do not appreciably affect the advantageous andunexpected characteristic of the tall oil pitch in the binder.

It is usually preferred that the cure controlling composition comprise,per 100 parts of the resin, from to 75 parts of tall oil pitch and from10 to 75 parts of pinewood pitch extract. Most desirably, the cureretarding composition comprises from 20 to 50 parts of tall oil pitchand from 20 to 50 parts of pinewood pitch extract.

It will be apparent that various changes and modifications can be madefrom the specific details set forth here in without departing from thespirit and scope of the invention as defined in the appended claims.

What I claim is:

1. A heat hardenable phenolic resin binder composition having a solidscontent from about 3 percent to about 24 percent, and that is an aqueousliquid blend of a phenol-formaldehyde resole, and a cure controllingcomposition comprising, per 100 parts of the phenolic resin, from 5parts to 100 parts of a tall oil pitch having a flash point from 400 F.to 550 F.

2. A heat hardenable phenolic resin binder composition having a solidscontent from about 3 percent to about 24 percent, and that is an aqueousliquid blend of a phenol-arnino compound-formaldehyde resole, and a curecontrolling composition comprising, per 100 parts of the phenolic resolefrom 5 parts to 100 parts of a tall oil pitch having a fiash point from400 F. to 550 F. and up to 100 parts of a pinewood pitch extract.

3. A heat hardenable phenolic resin binder composition having a solidscontent from about 3 percent to about 24 percent, and that is an aqueousliquid blend of a phenolic resole, and a cure controlling compositioncompris ing per 100 parts of the phenolic resole, from 1 0 parts toparts of a tall oil pitch having a flash point from 400 F. to 550 F. andfrom 10 parts to 75 parts of a pinewood pitch extract.

4. A heat hardenable phenolic resin binder composition having a solidscontent from about 3 percent to about 24 percent, and that is an aqueousliquid blend of a phenolic resole, and a cure controlling compositioncomprising, per parts of the phenolic resole, from 5 parts to 100 partsof a tall oil pitch having a hash point from 400 F. to 550 F. and up to100 parts of a pinewood pitch extract.

5. A heat hardenable phenolic resin binder composition having a solidscontent from about 3 percent to about 24 percent, and that is an aqueousliquid blend of a phenolic resole, and a cure controlling compositioncomprising, per 100 parts of the phenolic resole, from 20 parts to 50parts of a tall oil pitch having a flash point from 400 F. to 550 F. andfrom 20 parts to 50 parts of a pinewood pitch extract.

6. A method for producing a mass of intermeshcd vitreous fibers whichincludes the steps of depositing the fibers on a foraminous conveyor ina wool-like mass, depositing on the wool-like mass of fibers ahardenable phenolic resin binder composition having a solids contentform about 3 percent to about 24 perecent, and Which is an aqueousliquid blend of a phenolic resole, and a cure controlling compositioncomprising, per 100 parts of the phenolic resole, from 5 parts to 100parts of a tall oil pitch having a flash point from 400 F. to 550 F. andup to 100 parts of a pinewood pitch extract, and heating the mass offibers and associated binder composition to convert the latter to ahardened, cured condition.

7. A glass fiber coated with a thermoset phenolic resin bindercomposition which is the product of heat curing a blend of a phenolicresole, and, per 100 parts of the phenolic resole, from 5 parts to 100parts of a tall oil pitch having a flash point from 400 F. to 550 F. andup to 100 parts of a pinewood pitch extract.

8. A mass of intermeshed glass fibers bonded to one another at points ofcontact by a thermoset phenolic resin binder composition which is theproduct of heat curing a blend of a phenolic resole, and, per 100 partsof the phenolic resole, from 5 parts to 100 parts of a tall oil pitchhaving a flash point from 400 F. to 550 F. and up to 100 parts of apinewood pitch extract.

References Cited by the Examiner UNITED STATES PATENTS 2,391,368 12/1945 Underwood 260-25 2,424,074 7/ 1947 Bent et al 260-975 2,604,427 7/1952 Armstrong ct al.

2,620,319 12/ 1952 Rowe 26019 2,678,961 5/1954 Uhlig et al 260252,707,690 5/1955 Pearson 154101 2,801,198 7/1957 Morris et al 154433,048,508 8/1962 Boiney et al l54-43 3,056,708 10/1962 Ball 156-335 EARLM. BERGERT, Primary Examiner.

CARL F. KRAFFT, Examiner.

8. A MASS OF INTERMESHED GLASS FIBERS BONDED TO ONE ANOTHER AT POINTS OFCONTACT BY A THERMOST PHENOLIC RESIN BINDER COMPOSITION WHICH IS THEPRODUCT OF HEAT CURING A BLEND OF A PHENOLIC RESOLE, AND, PER 100 PARTSOF THE PHENOLIC RESOLE, FROM 5 PARTS TO 100 PARTS OF A TALL OIL PITCHHAVING A FLASH POINT FROM 400*F. TO 550*F. AND UP TO 100 PARTS OF APINEWOOD PITCH EXTRACT.